EP1670747B1 - Abtrennung von aromatischem amin aus einer phenolischen verbindung - Google Patents

Abtrennung von aromatischem amin aus einer phenolischen verbindung Download PDF

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Publication number
EP1670747B1
EP1670747B1 EP04794521A EP04794521A EP1670747B1 EP 1670747 B1 EP1670747 B1 EP 1670747B1 EP 04794521 A EP04794521 A EP 04794521A EP 04794521 A EP04794521 A EP 04794521A EP 1670747 B1 EP1670747 B1 EP 1670747B1
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EP
European Patent Office
Prior art keywords
hydroxide
base
sodium
glycol
phenolic compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP04794521A
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English (en)
French (fr)
Other versions
EP1670747A2 (de
Inventor
Carl Andrew Renner
Richard Frank Dubnansky
Freddison A. Parsons
Richard T. Stimek
Zhihong Wu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1670747A2 publication Critical patent/EP1670747A2/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/47—Toluidines; Homologues thereof

Definitions

  • the invention relates to a process for separation of an aromatic amine from a phenolic compound in a mixture comprising the aromatic amine and phenolic compound.
  • Aromatic amines are important industrial chemicals. They can be used to produce a very important class of industrial compounds such as azo dyes. Aromatic amines can be produced by chemical reduction of nitro compounds with a metal and acid such as, for example, iron or tin and hydrochloric acid or by catalytic hydrogenation using molecular hydrogen and a hydrogenation catalyst such as nickel or platinum. Nitro compounds can be readily made by direct nitration of aromatic compounds.
  • the product mixture produced by catalytic hydrogenation of an aromatic nitro compound generally comprises the desired amine, a corresponding phenolic compound, and unreacted aromatic nitro compound.
  • These by-products because of their color and deleterious effects on product properties, are undesirable and are difficult to separate from the amines by distillation. Therefore, there is an increasing need for the reduction of impurities to increase the amine purity.
  • Japanese Kokai Patent Application JP08295654 discloses a method of purification of aniline comprising contacting an aniline solution containing phenols with a diluted aqueous solution of an alkali. Said method involves liquid-liquid extraction and phase separation steps.
  • Japanese Kokai Patent Application JP49035341 discloses the purification of crude aromatic amines by contacting them with alkali before or during rectification. There is no disclosure of a molar ratio of alkali to phenolic compound of 0.5:1 to 10:1 in said reference.
  • a process for separation of an aromatic amine from a phenolic compound comprising contacting a product mixture with a base, to produce a base-treated mixture, introducing said base-treated mixture to a distillation apparatus, and distilling said base-treated mixture wherein said product mixture comprises an aromatic amine and a phenolic compounds, characterized in that the molar ratio of base to phenolic compound is in the range of from 0.5:1 to 10:1.
  • An aromatic amine can be produced by catalytic reduction or hydrogenation of an aromatic nitro compound, either under liquid phase or gas phase.
  • the reduction or hydrogenation can be carried out under any suitable conditions known to one skilled in the art, continuously, semi-continuously, or batch-wise.
  • a suitable condition can include a temperature in the range of from 30°C to 300°C, preferably 80°C to 250°C; a pressure that can accommodate the temperature such as 1 atm (103 kPa) to 20 atm (300 psig, 2000 kPa), preferably 150 kPa to 800 kPa; and for a sufficient period of time such as from one to 100 minutes.
  • Any hydrogenation catalysts known to one skilled in the art such as, for example, nickel, iron, platinum, copper, cobalt, palladium, iridium, and combinations of two or more thereof can be used in the production of aromatic amine.
  • a catalyst can be present in a catalytic amount effective to catalyze the hydrogenation or reduction and can be in the range of from 1 to 10,000 ppm (mg per kg) aromatic nitro compound.
  • a desired amine can have the formula of RAr(CH 2 )pNR 1 where Ar is an arylene group; R and each R 1 can be the same or different; each R 1 is independently selected from the group consisting of hydrogen, halogen, alkyl group, aryl group, and combinations of two or more thereof; and p is a number from 0 to 3.
  • Examples of amine products include, but are not limited to, aniline, toluidines, chloroanilines, bromoanilines, iodoanilines, chlorotoluidines, bromotoluidines, iodotoluidines, benzylamine, N-benzylamine, ethylanilines, fluoromethylanilines, chloromethylanilines, bromomethylanilines, and combinations of two or more thereof. These disclosed examples include all possible isomers.
  • aniline can be produced by the reduction of nitrobenzene with hydrogen either in the liquid phase using a supported hydrogenation catalyst such as nickel or precious metal, or in the gas phase using supported catalysts.
  • Phenol is a by-product, in trace amounts ranging from about 50 to about 1000 mg per kg amine product (ppm).
  • Aniline can also be produced by conversion of phenol in the Halcon process.
  • toluidine can be produced by reduction of nitrotoluene.
  • Nitrotoluene can be vaporized at a temperature in the range of from 150°C to 400°C to obtain a vapor or gas phase of nitrotoluene.
  • the vapor phase nitrotoluene is then introduced or fed to suitable equipment such as a gas phase vessel or reactor, preferably a fixed bed reactor containing a hydrogenation catalyst.
  • Hydrogen can be introduced into the equipment, preferably contemporaneously with the vapor phase nitrotoluene.
  • Impurities or by-products associated with the production of aromatic amines include, but are not limited to, unreacted nitro compounds, cyclohexanones, phenolic compounds, ketones, and combinations of two or more thereof.
  • phenolic compounds include, but are not limited to, phenol, cresols, chlorophenols, bromophenols, iodophenols, chlorotoluidines, bromotoluidines, iodotoluidines, benzylamine, N-benzylamine, ethylphenols, fluoromethylphenols, chloromethylphenols, bromomethylphenols and combinations of two or more thereof. These disclosed examples include all possible isomers.
  • Any unreacted nitro compound can be present in the product mixture in the range of from 0 to 1000 ppm and can be readily removed from the crude product by any means known to one skilled in the art such as, for example, distillation. Because such means are well known, the description ofwhich is omitted herein for the interest of brevity.
  • a desired amine compound contains lower than 500, preferably lower than 100, and more preferably lower than 50 parts per million (mg/kg) of such phenolic compound.
  • the product mixture (or crude product) is contacted with a base before it is distilled.
  • a base organic or inorganic
  • suitable bases can include, without limitation, lithium hydroxide, sodium hydroxide, sodium hydrosulfide, sodium bisulfide, potassium hydroxide, potassium hydrosulfide, potassium bisulfide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, sodium carbonate, sodium sulfide, sodium oxide, magnesium oxide, calcium oxide, calcium carbonate, sodium phenoxide, barium phenoxide, calcium phenoxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium bisulfide, tetraethylammonium bisulfide, and combinations of any two or more thereof. Potassium hydroxide and sodium hydroxide are preferred for they are readily available and inexpensive.
  • a base can be combined with the crude product at any concentration effective to reduce the phenolic compound contamination to the desired level disclosed above.
  • the molar ratio of base to phenolic compound is in the range of from 0.5:1 to 10:1, preferably 1:1 to 3:1 or 1:1 to 2:1.
  • the contacting of the crude product with a base can be carried out under any suitable conditions.
  • such condition can include a temperature in the range of from 0°C to 200°C, preferably 20°C to 50°C, a pressure that can accommodate the temperature such as 1 kPa to 300 kPa, preferably 10 kPa to 110 kPa, and for a sufficient period of time such as from 0.01 to 10,000 minutes.
  • Combining a base and an amine can also be carried out in the presence of a polyhydric alcohol.
  • polyhydric alcohol include, but are not limited to trimethylene glycol, triethylene glycol, glycerols, ethylene glycol, diethylene glycol, 1,2-propane diol, 1,3-profane diol, tripropylene glycol, polyethylene glycols, polypropylene glycols, and combinations of two or more thereof.
  • the polyhydric alcohol can be present in the base-amine combination in the range of from 1 to 10,000 mg per kg of the total combination.
  • a desired amine is recovered from the base-treated crude product (or product mixture) by distillation.
  • Suitable apparatus for the distillation is any customary apparatus as described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed. Vol. 7, John Wiley & Sons, New York, 1979, pages 870-881 , such as sieve plate columns, bubble cap columns or columns packed with arranged or dumped packing.
  • the distillation can be carried out in a single column or a plurality of columns, such as 2 or more columns. Any distillation techniques known to one skilled in the art can be used.
  • a suitable distillation can include a temperature in the range of from 100 to 400, preferably 100 to 250°C, a pressure that can accommodate the temperature such as 0.1 kPa to 200 kPa, preferably 5 kPa to 30 kPa, and for a sufficient period of time such as from 1 to 1500 minutes.
  • Example 1 This example illustrates reduction of phenol in aniline using KOH.
  • Example 2 This example shows reduction in phenol content in aniline using NaOH.
  • Example 2 To a distillation flask was added 100 ml of commercial aniline (phenol 122 ppm) and sodium hydroxide (35.7 mg) dissolved in 93 mg of water. The same procedure as Example 1 was followed. The distillate (75 ml) had a phenol content of 19 ppm. The phenol content of the material remaining in the distilling was 374 ppm.
  • Example 3 This example shows using KOH and unrectified crude aniline.
  • Example 4 This example illustrates using a polyhydric alcohol.
  • Example 5 This example shows treating o-toluidine with KOH.
  • Aqueous potassium hydroxide solution (45%; 0.1055 g) was charged into a three neck round bottom flask (500 ml) followed by 123.5g of o-toluidine (OTOL) containing 489.1 ppm of o-cresol.
  • OTOL was a commercial product commercially available from First Chemical Corp., Pascagoula, Mississippi.
  • An Aldrich Oldershaw column (ten stages) with a short path distillation head on top of the column was attached to the flask.
  • the mixture in the flask was agitated with a magnetic spin bar while vacuum was gradually pulled down to 90 mmHg (12 kPa).
  • the pot temperature was raised using a heating mantle to distill OTOL.
  • the typical distillation conditions were: pot temperature 130°C, overhead temperature 125°C, vacuum 90 mmHg (12 kPa). The distillation was stopped when boil up slowed down and the overhead temperature started falling. Distillate (108.5 g) was collected and was analyzed with GC to find o-cresol non-detectable.
  • Example 6 This example shows using a polyhydric alcohol to stabilize excess KOH.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (8)

  1. Verfahren für die Abtrennung eines aromatischen Amins von einer phenolischen Verbindung, umfassend das Kontaktieren einer Produktmischung mit einer Base unter Bildung einer basenbehandelten Mischung, das Einführen der basenbehandelten Mischung in einen Destillationsapparat und das Destillieren der basenbehandelten Mischung, wobei die Produktmischung ein aromatisches Amin und eine phenolische Verbindung umfasst, dadurch gekennzeichnet, dass das Molverhältnis von Base zu phenolischer Verbindung im Bereich von 0,5 : 1 bis 10 : 1 liegt.
  2. Verfahren nach Anspruch 1, wobei das Molverhältnis der Base zur phenolischen Verbindung im Bereich von 1 : 1 bis 4 : 1 liegt und die Base Lithiumhydroxid, Natriumhydroxid, Natriumhydrosulfid, Natriumbisulfid, Kaliumhydroxid, Kaliumhydrosulfid, Kaliumbisulfid, Calciumhydroxid, Magnesiumhydroxid, Natriumbicarbonat, Natriumcarbonat, Natriumsulfid, Natriumoxid, Magnesiumoxid, Calciumoxid, Calciumcarbonat, Natriumphenoxid, Bariumphenoxid, Calciumphenoxid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid, Tetramethylammoniumbisulfid, Tetraethylammoniumbisulfid oder Kombinationen irgendwelcher zwei oder mehrerer derselben ist.
  3. Verfahren nach Anspruch 2, wobei das Molverhältnis der Base zur phenolischen Verbindung im Bereich von 1 : 1 bis 2 : 1 liegt und die Base Kaliumhydroxid, Natriumhydroxid oder Kombinationen derselben ist.
  4. Verfahren nach Anspruch 1, 2 oder 3, wobei das Kontaktieren in Gegenwart des mehrwertigen Alkohols durchgeführt wird, der Trimethylenglykol, Triethylenglykol, Glycerin, Ethylenglykol, Diethylenglykol, 1,2-Propandiol, 1,3-Propandiol, Tripropylenglykol, Polyethylenglykol, Polypropylenglykol oder Kombinationen von zwei oder mehreren derselben ist.
  5. Verfahren nach Anspruch 1, wobei
    das Molverhältnis der Base zur phenolischen Verbindung im Bereich von 1 : 1 bis 4 : 1 liegt,
    die Base Lithiumhydroxid, Natriumhydroxid, Calciumhydroxid, Magnesiumhydroxid, Natriumbicarbonat, Natriumcarbonat, Natriumoxid, Magnesiumoxid, Calciumoxid, Calciumcarbonat, Tetramethylammoniumhydroxid, Tetraethylkammoniumhydroxid, Tetrapropylammoniumhydroxid, Tetramethylammoniumbisulfid, Tetraethylammoniumbisulfid oder Kombinationen irgendwelcher zwei oder mehrerer derselben ist; und
    das Amin Anilin, Toluidine, Chloraniline, Bromaniline, Iodaniline, Chlortoluidine, Bromtoluidine, lodtoluidine, Benzylamin, N-Benzylamin, Ethylaniline, Fluormethylaniline, Chlormethylaniline, Brommethylaniline oder Kombinationen von zwei oder mehreren derselben ist.
  6. Verfahren nach Anspruch 5, wobei das Kontaktieren in Gegenwart eines mehrwertigen Alkohols durchgeführt wird, der Trimethylenglykol, Triethylenglykol, Glycerin, Ethylenglykol, Diethylenglykol, 1,2-Propandiol, 1,3-Propandiol, Tripropylenglykol, Polyethylenglykol, Polypropylenglykol oder Kombinationen von zwei oder mehreren derselben ist.
  7. Verfahren nach Anspruch 6 zum Abtrennen von o-Cresol von o-Toluidin in einer Mischung, die o-Cresol und o-Toluidin umfasst, umfassend das Kontaktieren der Mischung mit Kaliumhydroxid unter Bildung einer basenbehandelten Mischung und das Destillieren der basenbehandelten Mischung.
  8. Verfahren nach Anspruch 7, wobei der mehrwertige Alkohol Polyethylenglykol ist.
EP04794521A 2003-10-10 2004-10-06 Abtrennung von aromatischem amin aus einer phenolischen verbindung Revoked EP1670747B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US51069003P 2003-10-10 2003-10-10
US10/798,083 US7049471B2 (en) 2003-10-10 2004-03-11 Separation of amine from a phenolic compound
PCT/US2004/033199 WO2005037767A2 (en) 2003-10-10 2004-10-06 Spearation of aromatic amine from a phenolic compound

Publications (2)

Publication Number Publication Date
EP1670747A2 EP1670747A2 (de) 2006-06-21
EP1670747B1 true EP1670747B1 (de) 2009-05-13

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ID=34426239

Family Applications (1)

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EP04794521A Revoked EP1670747B1 (de) 2003-10-10 2004-10-06 Abtrennung von aromatischem amin aus einer phenolischen verbindung

Country Status (9)

Country Link
US (1) US7049471B2 (de)
EP (1) EP1670747B1 (de)
JP (1) JP4672668B2 (de)
KR (2) KR20120040759A (de)
CN (1) CN1946675B (de)
DE (1) DE602004021122D1 (de)
HK (1) HK1101391A1 (de)
PT (1) PT1670747E (de)
WO (1) WO2005037767A2 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011081897A1 (de) 2011-08-31 2013-02-28 Bayer Materialscience Aktiengesellschaft Katalysator und Verfahren zur Herstellung von aromatischen Aminen in der Gasphase
US9447021B2 (en) 2012-03-23 2016-09-20 Covestro Deutschland Ag Process for the purification of aniline from gas phase hydrogenations
WO2021001424A1 (de) 2019-07-03 2021-01-07 Covestro Intellectual Property Gmbh & Co. Kg Verfahren zur reinigung von anilin

Families Citing this family (10)

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JP4552941B2 (ja) * 2006-01-17 2010-09-29 住友化学株式会社 アニリンの精製方法および製造方法
DE102006007620A1 (de) * 2006-02-18 2007-08-23 Bayer Materialscience Ag Verfahren zur Herstellung von Anilin
DE102006007619A1 (de) * 2006-02-18 2007-08-23 Bayer Materialscience Ag Verfahren zur Herstellung von Anilin
DE102006052989A1 (de) * 2006-11-10 2008-05-15 Bayer Materialscience Ag Verfahren zur Entfernung von Verbindungen mit phenolischen Hydroxygruppen aus aromatischen Aminen
DE102007039091A1 (de) * 2007-08-18 2009-02-19 Bayer Materialscience Ag Verfahren zur Reinigung von aromatischen Aminen
DE102009025374A1 (de) 2009-06-18 2010-12-23 Bayer Materialscience Ag Verfahren zur Herstellung von aromatischen Aminen
DE102010042731A1 (de) 2010-10-21 2012-04-26 Bayer Materialscience Aktiengesellschaft Verfahren zur Reinigung von Anilin aus Gasphasenhydrierungen
US8809587B2 (en) 2010-12-30 2014-08-19 Kellogg Brown & Root Llc Systems and methods for producing aromatic amines and removing phenol therefrom
EP3643699B1 (de) 2018-10-17 2021-09-22 Covestro Intellectual Property GmbH & Co. KG Verfahren zur reinigung von anilin
CN110252088B (zh) * 2019-06-25 2021-11-02 运城晋腾化学科技有限公司临猗分公司 一种尾气中苯胺的回收系统

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US3682782A (en) * 1968-07-11 1972-08-08 Halcon International Inc Reduced pressure distillation process for recovering aniline from phenolaniline mixtures
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US4267391A (en) * 1979-06-29 1981-05-12 Koppers Company, Inc. Process for obtaining para-cresol and meta-cresol from a mixture of methylated and ethylated phenols characterized by urea clathration of metal-cresol
US4491673A (en) * 1982-04-19 1985-01-01 Monsanto Company Production and separation of amines
JPS60199861A (ja) * 1984-03-23 1985-10-09 Mitsui Toatsu Chem Inc 芳香族ジアミン類の精製方法
US5192399A (en) * 1991-01-30 1993-03-09 E. I. Du Pont De Nemours And Company Purification of aminonitriles or diamines
IL98520A (en) * 1991-06-16 1996-10-31 Bromine Compounds Ltd Process for purifying diaminodiphenyl compounds
JP3804082B2 (ja) * 1995-04-27 2006-08-02 住友化学株式会社 アニリンの精製方法
DE10228594B4 (de) * 2002-06-26 2006-06-08 Lanxess Deutschland Gmbh Herstellung von farblosem Dibenzylamin

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011081897A1 (de) 2011-08-31 2013-02-28 Bayer Materialscience Aktiengesellschaft Katalysator und Verfahren zur Herstellung von aromatischen Aminen in der Gasphase
WO2013030221A1 (de) 2011-08-31 2013-03-07 Bayer Intellectual Property Gmbh Katalysator und verfahren zur herstellung von aromatischen aminen in der gasphase
US9266094B2 (en) 2011-08-31 2016-02-23 Bayer Intellectual Property Gmbh Catalyst and method for producing aromatic amines in the gas phase
US9447021B2 (en) 2012-03-23 2016-09-20 Covestro Deutschland Ag Process for the purification of aniline from gas phase hydrogenations
WO2021001424A1 (de) 2019-07-03 2021-01-07 Covestro Intellectual Property Gmbh & Co. Kg Verfahren zur reinigung von anilin

Also Published As

Publication number Publication date
WO2005037767A2 (en) 2005-04-28
WO2005037767A3 (en) 2005-06-23
US20050080294A1 (en) 2005-04-14
KR101186434B1 (ko) 2012-09-27
CN1946675B (zh) 2011-06-15
EP1670747A2 (de) 2006-06-21
KR20120040759A (ko) 2012-04-27
KR20060120020A (ko) 2006-11-24
CN1946675A (zh) 2007-04-11
JP4672668B2 (ja) 2011-04-20
DE602004021122D1 (de) 2009-06-25
PT1670747E (pt) 2009-08-05
US7049471B2 (en) 2006-05-23
HK1101391A1 (en) 2007-10-18
JP2007508312A (ja) 2007-04-05

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